Polymers and method of making the same



Sept. 27, 1938. H. e. SCHNEIDER POLYMERS AND METHOD OF MAKING THE SAME 7 Filed Dec. 8, 1934 t 8 7. v mi; 3 s V m T R :4: w a mvJ MW 0M MAM r 2 T; 7 mm EXCYHANGER 2 1 FEED AVA! .S TRIPPI/VG' TO WER a y +1, m M M. If. m m M n I L 4 W a a M E N M a .2: m 3 3 A f n WM, 2 u G L 2 a 3 A ll v s P s W. 6 A M b mm n O J-Jr L 8 I c 7 a. H

Patented Sept. 27, 1938 UNITED STATES PATENT OFFICE 2,181,196 POLYMERS AND METHOD OF MAKING THE Helmuth G. Schneider, Elizabeth, N. J., auignor to Standard Oil Development Company, a corporation of Delaware Application December 8, 1934, Serial No. 756,878

' 8 Claims. (Ci. 260-2) The present invention relates to the art of protions may be recompressed by pump l5, cooled at ducing valuable polymers from low boiling or iii and returned to the feed pipe II by pump Ila, gaseous hydrocarbons, and to such polymers Condensed steam is collected and removed by themselves and compositions containing the trap l8 and pipe l9. same, and especially tov lubricants comprising An oily medium may be introduced into tower the polymers either alone or in combination with H by line to collect the polymer; 9. part or all hydrocarbon oils. The invention will be fully unmay be added at the top or it may be added to derstood from the following description. line l2a which conducts the polymer into the The drawing represents in semi-diagrammatic tower, or by line 24 to line 2| conducting the form an apparatus for producing the polymer acproduct away from the tower. Line 22 allows up cording to the present invention. the removal of the product from the bottom of Referring to the drawing, numeral i represents towe 4 into wh ch e t s S pp through a pipe through which the polymerizable material, pipe 23. which will be referred to herein below as iso- Many variations may be made in the appabutylene, is forced either in a pure state or if deratus, for example a low boiling diluent may be 15 sired in admixture with a non-polymerizable dilselected, like propane or butane and it may be uent such as a saturated hydrocarbon, propane allowed to evaporate and chill the olefin during or butane or pentane. The material is in a lique-. Po y e e seperetien Polymer f fled condition and is forced by pump 2 into pipe h a d Catalyst y a be conducted using 8 2a through heat exchanger 3 and into a reaction Cen u to Separate the aqueous'cohstituehts vessel designated generally as 4. This vessel may rapidly from the polymer mixture, either with be of any desired type, the one shown being given or Wi h u the n u z i n pmerely as a suitable example. It may consist of The materials to be polymerized comprise the a shell 5 and narrow reaction tubes 6 connected ow boiling, Preferably normally gaseous OieflhS in series and jacketed by the shell. A refrigeratand in parti u p fi Su -8 B b t ing medium is kept in the shell so as to produce ene. which is pe ps t e ria r t i the low temperatures required. purpose. This particular substance, isobutylene,

Numeral i represents a pipe by which sulphuric may be used in a relatively P e t 1' acid is forced through a cooler 8 and valved a p s Obtained y the yd o of tertiary branch pipes la, lb, 10 and Id are provided to uty al h l, or t m be recovered fr m admit the acid from line ie to the reaction tubes cracked vapors and a m x d e y Wit butan so 6 and their ends so that a small amount of the and the various hydrocarbons of the same genacid may be added during the flow through the a boiling rangeseries of connected tubes. The suitable catalysts include strong and high- The reaction mixture passes through pipe 9 1y concentrated sulphuric acids, fuming sulphuric to exchanger 3 and then by pipe 9a to the recovacid, and even sulphur trioxide as well as chlorery system in which the polymer is removed from and Other halo sulphonic acids. It is highly 'dethe diluent, unreacted olefin and catalyst. Aquesirable to maintain the catalytic mate in qous alkali is forced into line 9a by means of line phase and Since the reaction takes Pl e at l0 and pump Illa and the entire mixture then very low temperatures,a solvent material capable passes through a bailled pipe II or equivalent of'maintaining the sulphuric acid catalyst in liqmixing device adapted to effect a rapid and comuid condition even at the lowest polymerization plete neutralization. It is preferable to add altemperatures is included. For this purpose sulcohol or acetone to the aqueous alkali so as to ohm-c ntai n s v fit are t be pr e red. prevent emulsions and to insure rapid and efiecm ng which may be included liquid sulphur ditive settling. oxide, sulphur halides, particularly the sulphur While it is preferred to neutralize the product chlorides such as mon0-, diand tetrachloride and before separation as outlined above this is not the sulphur oxy-halides, especially those which necessary and water or aqueous alcohol or acehave melting points well below -20 C. Carbon tone may be added by pipe I 0 as indicated. It disulphide may alsobe used for this purpose. The is then desirable to neutralize the polymer prodtemperature at which polymerization takes place not at a subsequent stage. should be below -20 C. and preferably below From the mixer H the product passes to asetand even as W as 0 C. tling drum l2 and the separation into layers oc- Under such conditions the reaction takes place curs herein. The lower layer contains the-aqueyielding polymerides of high molecular weight ous acidor neutralized acid and is removed by pipe and viscosity far above the well-known dimers, l3 and discarded. The oily or polymer layer is trimers and tetramers. It will be understood that rem ved y Pipe i2o to a strippin tower 4 low molecular weight fractions are produced likefrom which the volatile diluent and unreacted or wise but the important point here is that the partly reacted olefin is evaporated. Such fracheavy polymer fractions are obtained. It is m preferable to use low temperatures and to provide adequate provision to rapidly remove heat.

The more effective the removal of heat, the bet- 7 ter is the quality of the heavy polymer.

The product depends to a considerable extent on'the particular olefin polymerized and on the catalyst, and also on the temperature at which the reaction was carried out. Other things being equal, the lower the temperature the higher will be the molecular weight of the particular polymer. These polymers range widely in molecular weight, as indicated above, say from 1,000 to 5,000 or more. As produced, such polymers aremixtures in which the molecular weight varies and the above figures represent average molecularweights. The products in the lower end of the range are thick viscous liquids, tacky, colorless, tasteless and odorless when pure. They are readily soluble in petroleum oils, small amounts greatly increasing the viscosity thereof. The preferred starting materials, particularly isobutylene, produce a polymer which not only greatly increases viscosity but likewise favorably affects the viscositytemperature curve of the oil to which it is added, causing it to assume a flatter slope, which is, in effect, an increase in viscosity index. The higher polymers produced are plastic, sticky, somewhat elastic materials which are also colorless and odorless, freely soluble in mineral oils, and also greatly increasing the viscosity thereof. All of the present polymers may be decomposed by strong heat and they are characterized by breaking down almost exclusively to gases without production of solid carbonaceous residues.

Specific gravity 0.87 Viscosity 100 F "Sec. Saybolt 5,464 Viscosity 210 F d0 265.5

Viscosity index 103 II. A second run was made using twice as much catalyst as in Example I, at C. and for 15 minutes. The total crude polymer amountedto 62.3%. The polymer was precipitated from the diluent by adding acetone and the yield of this polymer was 44.3%. The polymer was then steamed to 400 F. removing about 10% so as to obtain a yield of 34%. The properties of the two polymers were as follows:

Precipitated with Steamed to 400 acetone F.

Specific gravity. 0. 88 0. 88 Viscosity at F 24, 785 47, 937 Viscosity at 210 F 852 1, 485 Viscosity index. H2 113 III. The heavy fractions of polymers prepared in Examples I and II were added to an S. A. E. 50 lubricating oil. The results were as follows:

It will be noted that the polymer made at 80 C. was heavy and superior in thickening and viscosity index increasing capacity, to the one prepared at -.36 C.

The present invention is not limited to any theory of the polymerization steps nor to any particular raw material, catalyst or catalyst solvent, but only to the following claims in which it is desired to claim all novelty inherent in the invention.

I claim:

1. An improved process for producing valuable high molecular weight polymers comprising maintaining a low molecular weight olefine in liquid phase in intimate contact with a polymerizing catalyst selected from the group consisting of sulphur trioxide and sulphuric, fuming sulphuric, and halo-sulphonic acids at a temperature below 20 C. and separating the catalyst from the resulting polymer.

2. Process according to claim 1, inwhich the catalyst is maintained in liquid phase by means of an inert solvent therefor.

3. Process according to claim 1, in which the catalyst is maintained in liquid phase by means of a sulphur-containing inert solvent therefor.

4. Process according to claim 1 in which said olefin is a normally gaseous olefin.

5. Process according to claim 1 in which said olefinis a normally gaseous alpha olefin.

6. Process according to claim 1 in which said olefin is isobutylene.

'7. An improved process for producing valuable high molecular weight polymers, comprising maintaining a low molecular weight olefin in liquid phrase, in intimate contact with a polymerizing catalyst selected from the group consisting of sulphur trioxide and sulphuric, fuming sulphuric, and halo-sulphonic acids, maintained in liquid phase by means of a solvent selected from the group of liquid sulphur dioxide, sulphur halides, sulphur oxyhalides of low melting points and carbon disulphide, at a temperature below about -20 C. and separating the catalyst from the polymer produced.

8. An improved process for producing valuable high molecular weight polymers of isobutylene, comprising maintaining the olefin in liquid phase in intimate contact with fuming sulphuric acid at a temperature from 20 C. to -80 C. in the presence of liquid sulphur dioxide; capable of maintaining the fuming sulphuric acid in a liquid condition.

HELMUTH G. SCHNEIDER. 

